WO1999014273A1 - Melanges de polymeres durcis - Google Patents

Melanges de polymeres durcis Download PDF

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Publication number
WO1999014273A1
WO1999014273A1 PCT/US1998/017889 US9817889W WO9914273A1 WO 1999014273 A1 WO1999014273 A1 WO 1999014273A1 US 9817889 W US9817889 W US 9817889W WO 9914273 A1 WO9914273 A1 WO 9914273A1
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WIPO (PCT)
Prior art keywords
blend
polymer
weight percent
ethylene
component
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PCT/US1998/017889
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English (en)
Inventor
John M. Warakomski
David H. Bank
Thoi H. Ho
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The Dow Chemical Company
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Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to AT98942286T priority Critical patent/ATE205235T1/de
Priority to EP98942286A priority patent/EP1015517B1/fr
Priority to CA002301701A priority patent/CA2301701A1/fr
Priority to DE69801587T priority patent/DE69801587T2/de
Priority to JP2000511816A priority patent/JP2001516786A/ja
Priority to AU90379/98A priority patent/AU9037998A/en
Priority to KR1020007002583A priority patent/KR20010023899A/ko
Publication of WO1999014273A1 publication Critical patent/WO1999014273A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to toughened blends of syndiotactic monovinylidene aromatic and amide polymers.
  • Blends of syndiotactic monovinylidene aromatic polymers for example syndiotactic polystyrene (SPS) and polyamides, for example nylon, are known in the art, having excellent impact and heat resistance.
  • these types of blends are toughened using various rubbery polymers.
  • U.S. 5,395,890 issued to Nakano et al. discloses a resin composition containing SPS, nylon and optionally a rubbery block polymer.
  • US-A-5,219,940 discloses SPS and polyamide blends, optionally containing block or grafted rubbers.
  • US-A-5,270,353 discloses blends of SPS with nylon toughened with block and maleated block copolymers.
  • block copoiymer rubbers are expensive and add significant cost to the blends.
  • the present invention is a polymer blend comprising: a) a syndiotactic monovinylidene aromatic polymer, b) a polyamide, c) a compatibilizing polymer for a) and b), d) a rubbery polyolefin impact modifier, optionally extended with oil, e) a domain forming rubbery polymer, f) a polar group fu ⁇ ctionalized rubbery polyolefin, and g) optionally, a compatibilizing polymer for a) and d).
  • These blends are more economical than those of the prior art, using polyolefin elastomers as toughening agents, and can be used in markets where high heat resistance is required such as in automotive applications and in applications where nylon alone has been typically used.
  • the present invention is a toughened blend of a syndiotactic monovinylidene aromatic polymer and a poiyamide.
  • stereotactic refers to polymers having a stereoregular structure of greater than 90 percent syndiotactic, preferably greater than 95 percent syndiotactic, of a racemic triad as determined by 13 C nuclear magnetic resonance spectroscopy.
  • Monovinylidene aromatic polymers are homopolymers and copolymers of vinyl aromatic monomers, that is, monomers whose chemical structure possess both an unsaturated moiety and an aromatic moiety.
  • the preferred vinyl aromatic monomers have the formula
  • H 2 C CR-Ar; wherein R is hydrogen or an alkyl group having from 1 to 4 carbon atoms, and Ar is an aromatic radical of from 6 to 10 carbon atoms.
  • vinyl aromatic monomers are styrene, alpha-methylstyrene, ortho-methylstyrene, meta- methylstyrene, para-methylstyrene, vinyl toluene, para-t-butylstyrene, vinyl naphthalene, and divinylbenzene.
  • Syndiotactic polystyrene is the currently preferred syndiotactic monovinylidene aromatic polymer.
  • the Mw of the syndiotactic monovinylidene aromatic polymer used in the blend of the present invention is not critical, but is typically from 200,000 to 450,000.
  • the amount of syndiotactic monovinylidene aromatic polymer present in the blend of the present invention is typically from 10 to 90 weight percent based on the total weight of the blend, preferably from 20 to 80 weight percent and more preferably from 30 to 60 weight percent.
  • the polyamide of component b) of the blend of the present invention can be any thermoplastic polyamide.
  • Typical polyamides include polyamide-4; polyamide-6; polyamide-4,6; polyamide-6,6; polyamide-3,4; polyamide-1 ,2; poiyamide-1 ,1 ; polyamide-6,10; polyamide purified from terephthalic acid and 4,4' diaminocyciohexylmethane; polyamide purified from azelaic acid, adipic acid and
  • the Mw of the polyamide is not critical but is typically from 40,000 to 60,000.
  • the amount of polyamide present in the blend of the present invention is typically from 10 to 90 weight percent based on the total weight of the blend, preferably from 20 to 80 weight percent and more preferably from 30 to 60 weight percent.
  • the syndiotactic monovinylidene aromatic polymer a), and polyamide b) are typically present in the blend of the present invention in ratios of from 5:95 to 95:5 based on only those two components. Preferably in ratios of 20:80 to 80:20, more preferably 30:70 to 70:30 and most preferably 40:60 to 60:40.
  • Component c) of the present invention is a polymer which acts as a compatibilizer for the syndiotactic monovinylidene aromatic polymer and the polyamide. This can be any material which has a functionality compatible with the monovinylidene aromatic and a functionality compatible with the amide functional groups. Typically, the compatibilizer is a polyarylene ether having such functionalities.
  • Polyarylene ethers are a known class of polymer having been previously described in US-A-3,306,874, US-A-3,306,875, US-A-3,257,357, and US-A-3,257,358.
  • a preferred polyarylene ether is poly(2,6-dimethyl-1 ,4- phenylene)ether.
  • the polyphenylene ethers are normally prepared by an oxidative coupling reaction of the corresponding bisphenol compound.
  • Preferred polyarylene ethers are polar group functionalized polyarylene ethers, which are a known class of compounds prepared by contacting polar group containing reactants with polyarylene ethers. The reaction is normally conducted at an elevated temperature, preferably in a melt of the polyarylene ether, under conditions to obtain homogeneous incorporation of the functionalizing reagent. Suitable temperatures are from 150°C to 300°C.
  • Suitable polar groups include the acid anhydrides, acid halides, acid amides, sulfones, oxazolines, epoxies, isocyanates, and amino groups.
  • Preferred polar group containing reactants are compounds having up to 20 carbons containing reactive unsaturation, such as ethylenic or aliphatic ring unsaturation, along with the desired polar group functionality.
  • Particularly preferred polar group containing reactants are dicarboxylic acid anhydrides, most preferably maieic anhydride.
  • the amount of polar group functionalizing reagent employed is from 0.01 percent to 20 percent, preferably from 0.5 to 15 percent, most preferably from 1 to 10 percent by weight based on the weight of polyarylene ether.
  • the reaction may be conducted in the presence of a free radical generator such as an organic peroxide or hydroperoxide agent if desired.
  • a free radical generator such as an organic peroxide or hydroperoxide agent if desired.
  • Preparation of polar group functionalized polyarylene ethers have been previously described in US-A-3,375,228, US-A-4,771 ,096 and US-A-4,654,405.
  • the amount of polyarylene ether employed in the present resin blend is beneficially from 0.1 to 20 weight percent, preferably from 0.2 to 10, more preferably from 0.5 to 5 weight percent based on the total blend weight.
  • the polar group modified polyarylene ether may be in the form of a coating applied to the outer surface of a reinforcing agent to impart added compatibility between the reinforcing agent and the polymer matrix.
  • the polar group modified polyarylene ether so utilized may be in addition to further amounts of polyarylene ether or polar group modified polyarylene ether also incorporated in the blend.
  • the surface coating is suitably applied to the reinforcing agent by contacting the same with a solution or emulsion of the polar group functionalized polyarylene ether.
  • Suitable solvents for dissolving the polar group functionalized polyarylene ether to form a solution or for use in preparing an emulsion of a water-in-oil or oii-in-water type include methylene chloride, trichloromethane, trichloro-ethylene and trichioroethane.
  • concentration of polar group functionalized polyarylene ether in the solution or emulsion is from 0.1 weight percent to 20 weight percent, preferably 0.5 to 5 percent by weight.
  • the liquid vehicle is removed by, for example, evaporation, devolatilization or vacuum drying.
  • the resulting surface coating is desirably from 0.001 to 10 weight percent of the uncoated reinforcing agent weight.
  • the blend of the present invention is toughened using two rubbery polyolefins, one for each polymer phase of a) (syndiotactic monovinylidene aromatic polymer) and b)(polyamide).
  • Component d) is a rubbery polyolefin which toughens the syndiotactic vinyl aromatic phase and can be any elastomeric polyolefin.
  • Elastomeric polyolefins include any polymer comprising one or more C 2 -2o ⁇ -olefins in polymerized form, having Tg less than 25°C, preferably less than 0°C.
  • Examples of the types of polymers from which the present elastomeric polyolefins are selected include homopolymers and copolymers of ⁇ -oiefins, such as ethylene/propyiene, ethylene/1-butene, ethylene/1-hexene or ethylene/1 -octene copolymers, and terpolymers of ethylene, propylene and a comonomer such as hexadiene or ethylidenenorbomene.
  • Grafted derivatives of the foregoing rubbery polymers such as polystyrene-, maleic anhydride-, porymethylmethacrylate- or styrene/methyl methacrylate copolymer-grafted elastomeric polyolefins may also be used.
  • the elastomeric polyolefins are preferably softened by incorporation of an aliphatic oil to extend the polyolefin phase, making it softer and more readily dispersed into the syndiotactic vinyl aromatic polymer phase.
  • the extending oils also referred to as paraffinic/naphthenic oils, are usually fractions of refined petroleum products having less than 30 percent by weight of aromatics (by clay-gel analysis) and having viscosities between 100 and 500 SSU at 100°F (38°C).
  • extending oils include SHELLFLEX® oils, numbers 310, 371 and 311 (which is a blend of 310 and 371), available from Shell Oil Company or DrakeolTM, numbers 34 or 35, available from Penreco division of Pennzoil Products Company.
  • the amount of extending oil employed varies from 0.01 to 35.0 weight percent, preferably from 0.1-25 percent, most preferably from 2-25 weight percent based on the weight of the elastomeric polyolefin.
  • Preferred elastomeric polyolefins for use herein are such polymers that are characterized by a narrow molecular weight distribution and a uniform branching distribution.
  • Preferred elastomeric polyolefins are linear or substantially linear ethylene interpolymers having a density from 0.85 to 0.93 g/cm 3 , a melt index from 0.1 to 5 g/10 min, and a polydispersity of from 1.8 to 5.
  • Such polymers are preferably those prepared using a Group 4 metal constrained geometry complex by means of a continuous solution polymerization process, such as disclosed in US-A-5,272,236 and US-A-5,278,272.
  • More preferred elastomeric polyolefins have a density of from 0.860 to 0.920 g/cm 3 , more preferably from 0.865 to 0.915 g/cm 3 , and especially less than or equal to 0.910 g/cm 3 .
  • interpolymer refers to polymers prepared by the polymerization of at least two different monomers.
  • the generic term interpolymer thus embraces copolymers, usually employed to refer to polymers prepared from two different monomers, and polymers prepared from more than two different monomers.
  • polymer or interpolymer as comprising or containing certain monomers, it is meant that such polymer or interpolymer comprises or contains polymerized therein units derived from such a monomer.
  • the derivative of this unit as incorporated in the polymer is -CH 2 -CH r .
  • melt index values are specified in the present application without giving measurement conditions, the melt index as defined in ASTM D-1238, Condition 190°C/2.16 kg (formerly known as “Condition (E)” and also known as 12) is meant.
  • substantially linear ethylene polymer or interpolymer as used herein means that, in addition to the short chain branches attributable to intentionally added ⁇ -olefin comonomer incorporation in interpolymers, the polymer backbone is substituted with an average of 0.01 to 3 long chain branches/1000 carbons, more preferably from 0.01 long chain branches/1000 carbons to 1 long chain branches/1000 carbons, and especially from 0.05 long chain branches/1000 carbons to 1 long chain branches/1000 carbons.
  • Long chain branching is defined herein as a chain length of at least 1 carbon less than the number of carbons in the longest intentionally added ⁇ -olefin comonomer
  • short chain branching is defined herein as a chain length of the same number of carbons in the branch formed from any intentionally added ⁇ -olefin comonomer after it is incorporated into the polymer molecule backbone.
  • an ethylene/1 -octene substantially linear polymer has backbones substituted with long chain branches of at least 7 carbons in length, but it also has short chain branches of only 6 carbons in length resulting from polymerization of 1 - octene.
  • deGroot and Chum found that the presence of octene does not change the hydrodynamic volume of the polyethylene samples in solution and, as such, one can account for the molecular weight increase attributable to octene short chain branches by knowing the mole percent octene in the sample. By deconvoluting the contribution to molecular weight increase attributable to 1 -octene short chain branches, deGroot and Chum showed that GPC-DV may be used to quantify the level of long chain branches in substantially linear ethylene/1 -octene copolymers.
  • the empirical effect of the presence of long chain branching in the substantially linear ethylene/ ⁇ -oiefin interpolymers used in the invention is manifested as enhanced rheoiogical properties which are quantified and expressed herein in terms of gas extrusion rheometry (GER) results, and/or in terms of melt flow ratio (110/12) increase.
  • GER gas extrusion rheometry
  • linear means that the polymer lacks measurable or demonstrable long chain branches, that is, the polymer is substituted with an average of less than 0.01 long branches/1000 carbons.
  • substantially linear ethylene interpolymers as used herein are further characterized as having
  • the processing index is measured at a temperature of 190°C, at nitrogen pressure of 2500 psig (17 Mpa) using a 0.0296 inch (0.0117 cm) diameter, 20:1 LJD die with an entrance angle of 180°.
  • the GER processing index is calculated in millipoise units from the following equation:
  • PI 2.15x10 6 dynes/cm 2 /(1000 x shear rate), where: 2.15x10 6 dynes/cm 2 is the shear stress at 2500 psi, (17 Mpa) and the shear rate is the shear rate at the wall represented by the following equation: 32Q7(60 sec/min)(0.745)(diameter x 2.54 cm/in) 3 , where Q' is the extrusion rate (g/min), 0.745 is the melt density of the polyethylene (g/cm 3 ), and diameter is the orifice diameter of the capillary (inches).
  • the PI is the apparent viscosity of a material measured at apparent shear stress of 2.15x10 6 dyne/cm 2 .
  • the PI is less than or equal to 70 percent of that of a comparative linear olefin polymer having an 12 and Mw/Mn each within 10 percent of the substantially linear ethylene polymers.
  • the rheoiogical behavior of substantially linear ethylene polymers can also be characterized by the Dow Rheology Index (DRI), which expresses a polymer's
  • DRI values range from 0, for polymers which do not have any measurable long chain branching (for example, TAFMERTM products available from Mitsui Petrochemical industries and EXACTTM products available from Exxon Chemical Company), to 15 and is independent of melt index.
  • DRI provides improved correlations to melt elasticity and high shear flowabiiity relative to correlations of the same attempted with melt flow ratios.
  • DRI is preferably at least 0.1 , and especially at least 0.5, and most especially at least 0.8. DRI can be calculated from the equation:
  • DRI 3652879 x ⁇ ° 1 -""" ( ⁇ o-iyiO
  • ⁇ o is the characteristic relaxation time of the material
  • ⁇ o is the zero shear viscosity of the material.
  • Baseline determination of viscosity and shear rate data are obtained using a Rheometric Mechanical Spectrometer (RMS-800) under dynamic sweep mode from 0.1 to 100 rad/sec at 190°C and a Gas Extrusion Rheometer (GER) at extrusion pressures from 1000 psi to 5000 psi (6.89 to 34.5 MPa), which corresponds to shear stress from 0.086 to 0.43 MPa, using a 0.0754 mm diameter, 20:1 L D die at 190°C.
  • Specific material determinations can be performed from 140°C to 190°C as required to accommodate melt index variations.
  • An apparent shear stress versus apparent shear rate plot is used to identify the melt fracture phenomena. According to Ramamurthy in Journal of Rheology, Vol. 30(2), pp. 337-357, 1986, above a certain critical flow rate, the observed extrudate irregularities may be broadly classified into two main types: surface melt fracture and gross melt fracture.
  • onset of surface melt fracture is characterized as the beginning of losing extrudate gloss at which the surface roughness of extrudate can only be detected by 40x magnification.
  • the critical shear rate at onset of surface melt fracture for the substantially linear ethylene polymers is at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear ethylene polymer having the same 12 and Mw/Mn.
  • Gross melt fracture occurs at unsteady flow conditions and ranges in detail from regular (alternating rough and smooth or helical) to random distortions.
  • the critical shear rate at onset of surface melt fracture (OSMF) and onset of gross melt fracture (OGMF) will be used herein based on the changes of surface roughness and configurations of the extrudates extruded by a GER.
  • the substantially linear ethylene polymers used in the invention are also characterized by a single DSC melting peak.
  • the single melting peak is determined using a differential scanning calorimeter standardized with indium and deionized water.
  • the method involves 5 to 7 mg sample sizes, a "first heat” to 150°C which is held for 4 minutes, a cool down at 10°C/minute to -30°C which is held for 3 minutes, and heated at 10°C/minute to 150°C for the "second heat.”
  • the single melting peak is taken from the "second heaf heat flow versus temperature curve. Total heat of fusion of the polymer is calculated from the area under the curve.
  • the single melting peak may show, depending on equipment sensitivity, a "shoulder” or a "hump” on the low melting side that constitutes less than 12 percent, typically less than 9 percent, and more typically less than 6 percent of the total heat of fusion of the polymer.
  • Such an artifact is observable for other homogeneously branched polymers such as EXACTTM resins (made by Exxon Chemical Company) and is discerned on the basis of the slope of the single peak varying monotonically through the melting region of the artifact.
  • EXACTTM resins made by Exxon Chemical Company
  • Such an artifact occurs within 34°C, typically within 27°C, and more typically within 20°C, of the melting point of the single peak.
  • the heat of fusion attributable to an artifact can be separately determined by specific integration of its associated area under the heat flow versus temperature curve.
  • polydispersity as used herein is a synonym for the term “molecular weight distribution” which is determined as follows: The polymer or composition samples are analyzed by gel permeation chromatography (GPC) on a Waters 150°C high temperature chromatographic unit equipped with three mixed porosity columns (Polymer Laboratories 103, 104, 105, and 106), operating at a system temperature of 140°C.
  • the solvent is 1 ,2,4- trichlorobenzene, from which 0.3 percent by weight solutions of the samples are prepared for injection.
  • the flow rate is 1.0 milliliters/minute and the injection size is 200 microliters.
  • the molecular weight determination is deduced by using narrow molecular weight distribution polystyrene standards (from Polymer Laboratories) in conjunction with their elution volumes.
  • Mw ⁇ i wi • Mi, where wi and Mi are the weight fraction and molecular weight, respectively, of the ith fraction eiuting from the GPC column.
  • the rubbery polyolefin impact modifier d) is typically present in the blend of the present invention in amounts from 0.1 to 10 weight percent based on the total blend weight, preferably from 0.5 to 7, more preferably from 1 to 5 weight percent.
  • the rubbery polyolefin impact modifier is typically from 2 to 25 weight percent of the syndiotactic monovinylidene aromatic polymer phase.
  • syndiotactic monovinylidene aromatic polymer of a) and rubbery polyolefin elastomer of d) are typically present in ratios of from 50:50 to 99:1 based on only those two components.
  • Component e) of the present invention comprises one or more domain forming rubbery polymers.
  • Such rubbery polymers are suitably chosen in order to impart impact absorbing properties to the polymer composition and enhance the toughening performance of the rubbery polyolefin elastomer of d).
  • Such polymers having high melt viscosity are not drawn into extremely thin sections by the shear forces of the compounding process, and retain greater ability to reform discrete rubber particles more closely resembling spherical particles upon discontinuance of shearing forces.
  • the domain forming rubbery polymer beneficially should retain sufficient elastic memory to reform droplets in the melt when shearing forces are absent.
  • One beneficial result of the present combination appears to be that the domain forming rubbery polymer is selected to be compatible with the rubbery polyolefin elastomer into which it mostly partitions under processing condition. Within such domain, the shearing forces are not as detrimental to rubber domain formation as when the domain forming rubbery polymer is incorporated directly into the matrix resin.
  • higher molecular weight domain forming rubbery polymers possess increased melt viscosity.
  • preferred domain forming rubbery polymers are those having Mw from 100,000 to 400,000 Daltons, more preferable from 150,000 to 300,000 Daltons, and having Tg less than 25°C, more preferably less than 0°C.
  • Weight average molecular weights recited herein are apparent values based on a polystyrene standard, derived from gel permeation chromatography data, and not corrected for hydrodynamic volume differences between polystyrene and other polymeric components.
  • Low molecular weight block copolymers that is, polymers having molecular weight less than 100,000 Daltons, have been found to possess insufficient melt viscosity to achieve the desired rubber droplet formation.
  • Most preferred domain forming rubbery polymers are those having a melt flow rate, Condition X (315°C, 5.0 Kg) from 0 to 0.5 g/10 min.
  • Typical domain forming rubbery polymers include lower molecular weight (higher melt index) copolymers of styrene and a rubber such as butadiene or isoprene, including styrene/butadiene/styrene triblock copolymers, hydrogenated styrene/butadiene styrene triblock copolymers, styrene/butadiene block copolymers, styrene/isoprene block copolymers, or a hydrogenated versions thereof.
  • Preferred block copolymers are those containing from 20 to 75 weight percent styrene with the remainder comprising butadiene, isoprene or a hydrogenated derivative thereof.
  • the domain forming rubbery polymer may also act as the compatibilizer between the syndiotactic monovinylidene aromatic polymer a) and the rubbery polyolefin elastomer d).
  • such domain forming rubbery block copolymers will act as a compatibilizer if the copolymer contains a compatibilizing amount of monovinylidene aromatic block.
  • a compatibilizing amount will be at least 30 weight percent, typically at least 40 weight percent, preferably at least 50 weight percent, more preferably at least 60 weight percent and most preferably at least 70 weight percent monovinylidene aromatic block.
  • a small quantity of a low density polyethylene may also be utilized as the domain forming rubbery polymer.
  • Suitable low density polyethylene polymers include linear interpolymers of ethylene and at least one further ⁇ -olefin, most preferred are homogeneous linear interpolymers.
  • Preferred ⁇ -olefins have from 3 to 20 carbon atoms. More preferred ⁇ -olefins have from 3 to 8 carbon atoms.
  • Exemplary comonomers include propene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1 -hexene, and 1 -octene.
  • the low density polyethylene may also contain, in addition to the ⁇ -oiefin, one or more further comonomers, such as diolefins, ethylenically unsaturated carboxylic acids (both mono- and difunctional) as well as derivatives of these acids, such as esters and anhydrides.
  • additional comonomers are acrylic acid, methacrylic acid, vinyl acetate and maieic anhydride.
  • the low density polymers suitable for use in the present compositions can be further characterized by their homogeneity and degree of long chain branching.
  • Preferred quantities of the domain forming rubbery polymer are from 2 to 30, most preferably 5 to 25 weight percent based on the weight of the rubbery polyolefin elastomer d).
  • the rubbery polyolefin elastomer and domain forming rubbery polymer (components d) and e)) are typically present in ratios of from 60:40 to 100:0 based on only those two components, preferably 70:30 to 95:5 and more preferably 80:20 to 90:10.
  • the domain forming rubbery polymer is typically present in amounts of 0.1 to
  • the rubbery polyolefin elastomer of c) and domain forming rubbery polymer of e) are typically present in ratios of from 60:40 to 99:1 based on only those two components, preferably 70:30 to 95:5, and more preferably 85:15 to 90:10.
  • the polyamide phase b) is toughened by a polar group functionalized polyolefin, Component f). Typical functional groups include carboxylic acids, carboxylic acid esters, anhydrides, amines, amides, epoxies, maleimides and any other functional group which will compatibilize the polyolefin with the polyamide phase.
  • the preferred functional groups are those groups which can react with the polyamide during melt blending, such as amines, epoxies, anhydrides and carboxylic acids.
  • the functionalized polyolefin is a maleated polyolefin.
  • Maleated polyolefins are known in the art and are typically obtained by grafting maleic anhydride onto the polyolefin backbone.
  • the polyolefin may be the same as the rubbery polyolefin elastomer used to toughen the syndiotactic monovinylidene aromatic phase or different.
  • Typical maleated polyolefins include maleated alpha- olefins such as ethylene-octene copolymer, ethylene-hexene copolymer, and ethylene-heptene copolymer.
  • Maleation of the polyolefin may be done by in the melt, in solution, or in the solid state, and the process can be either continuous or batch.
  • Various free radical initiators, including peroxides and azo compounds may be used to facilitate the maleation. All of these processes are well know and fully described in the art.
  • Maleating agents can include anhydrides such as maleic anhydride, unsaturated dicarboxylic acids such as fumaric acid or other agents listed in columns 6-7 of US-A-5,219,940.
  • the amount of polar group functionalized rubbery polyolefin in the blend of the present invention is typically from 0.1 to 10 weight percent based on the total weight of the blend, preferably from 0.5 to 7, and more preferably from 1 to 5 weight percent.
  • the amount of polar group functionalized rubbery polyolefin present based on the amount of polyamide is typically from 2 to 25 weight percent.
  • the polyamide of b) and polar group-functionaiized polyolefin elastomer of f) are typically present in ratios of from 50:50 to 99:1 based on only those two components, preferably 80:20 to 99:1 , more preferably 85:15 to 98:2 and most preferably 90:10 to 97:3.
  • a compatibilizing polymer, Component g) which acts as a compatibilizer for the syndiotactic monovinylidene aromatic polymer a) and the rubbery polyolefin elastomer d) is included in the blend of the present invention.
  • a compatibilizing polymer is necessary if the domain forming rubbery polymer is not a compatibilizing polymer for components a) and d).
  • a compatibilizing polymer typically comprises a block copolymer such as a lower molecular weight (higher melt index) styrene/butadiene/styrene triblock copolymer, a hydrogenated styrene/butadiene/styrene triblock copolymer, or a styrene/butadiene diblock copolymer, a styrene/isoprene block copolymer, or a hydrogenated derivative thereof.
  • Preferred block copolymers are those containing from 45 to 75 weight percent styrene with the remainder comprising butadiene, isoprene or a hydrogenated derivative thereof.
  • a typical ratio of rubbery polyolefin impact modifier of d) to domain forming rubbery polymer of e) to compatibilizing agent of g) is 75:15:10 by weight.
  • Nucleators may also be used in the blend of the present invention and are compounds capable of reducing the time required for onset of crystallization of the syndiotactic monovinylidene aromatic polymer upon cooling from the melt.
  • Nucleators provide a greater degree of crystallinity in a molding resin and more consistent levels of crystallinity under a variety of molding conditions. Higher levels of crystallinity are desired in order to achieve increased chemical resistance. In addition crystal morphology may be desirably altered.
  • suitable nucleators for use herein are metal salts, especially aluminum salts of organic acids or phosphonic acids. Especially preferred compounds are aluminum salts of benzoic acid and C ⁇ - 10 alkyl substituted benzoic acid derivatives. A most highly preferred nucleator is aluminum tris(p-tert-butyl)benzoate.
  • the amount of nucleator used should be sufficient to cause nucleation and the onset of crystallization in the syndiotactic vinylaromatic polymer in a reduced time compared to compositions lacking in such nucleator.
  • Preferred amounts are from 0.1 to 5 weight percent, preferably from 0.1 to 3 weight percent and most preferably from 0.2 to 1 weight percent based on the weight of component a).
  • Suitable reinforcing agents include any mineral, glass, ceramic, polymeric or carbon reinforcing agent. Such material may be in the shape of fibers having a length to diameter ratio (IJD) of greater than 5. Preferred particle diameters are from 0.1 micrometers to 1 millimeter. Preferred reinforcing agents are glass fibers, glass roving or chopped glass fibers having lengths from 0.1 to 10 millimeters and L/D from 5 to 100.
  • Suitable fillers include nonpolymeric materials designed to reduce the coefficient of linear thermal expansion of the resulting material, to provide color or pigment thereto, to reduce the flame propagation properties of the composition, or to otherwise modify the composition's physical properties. Suitable fillers include mica, talc, chalk, titanium dioxide, clay, alumina, silica, glass microspheres, and various pigments. Preferred fillers are in the shape of particulates having (IJD) less than 5.
  • the amount of reinforcing agent or filler employed is preferably from 10 to 50 weight percent, more preferably from 20 to 40 weight percent based on the total weight of the filled composition.
  • the reinforcing agent may include a surface coating of a sizing agent or similar coating which, among other functions, may promote adhesion between the reinforcing agent and the remaining components, especially the matrix, of the composition.
  • Suitable sizing agents may contain amine, aminosilane, epoxy, and aminophosphine functional groups and contain up to 30 nonhydrogen atoms.
  • Additional additives such as blowing agents, extrusion aids, antioxidants, plasticizers, stabilizers, ignition resistant additives, and lubricants, may also be included in the composition in amounts up to 10 percent, preferably up to 5 percent, by weight, based on final composition weight.
  • the blend of the present invention is typically produced by compounding all the components in a mixing device such as an extruder.
  • a mixing device such as an extruder.
  • Mechanical mixing devices such as extruders, ribbon blenders, solution blending or any other suitable device or technique may be utilized. All components (syndiotactic monovinylidene aromatic polymer, non-functionalized polyolefin, polar functionalized polyolefin, domain forming rubbery polymer, compatibilizing polymer, and optional components such as fillers, nucleating agents, and stabilizers) can be compounded together in an extruder.
  • the oil included in the polyolefin phase can be precompounded into the polyolefin elastomer in a separate step or added during the compounding of the blend.
  • compositions of the present invention are prepared by combining the respective components under conditions to provide uniform dispersal of the ingredients.
  • the polar group functionalized polyarylene ether and polar group functionalized polyolefin may be prepared in situ by reacting the polar group reactant with the polyphenylene ether and further incorporating the molten product directly into the finished blend.
  • the following examples are provided to illustrate the present invention. The examples are not intended to limit the scope of the present invention and they should not be so interpreted. Amounts are in weight parts or weight percentages unless otherwise indicated. EXAMPLE 1
  • the formulations in Table 1 are prepared using the following procedure.
  • the polyolefin (PO) elastomer is first compounded with 25 percent Drakeol 34 mineral oil in a separate step on a 40 mm Berstorff twin screw extruder at 180-200°C, at a rate of 200 pounds hour, and 250 rpm. All additional components are then tumble blended together and compounded through a Werner Pfleiderer ZSK30 twin screw extruder. Barrel temperature settings of 275-280°C, 35 pounds per hour, and screw speed 350 rpm are used. Vacuum (24 inches mercury) is applied at the vent before the die. Strands are cooled in a water bath and peiletized.
  • Injection molding is done on a Mannesmann Demag D 100-275 injection molding machine with barrel temperatures of 305-315°C and mold temperature of 150°C.
  • Tensile, instrumented impact, and Izod impact testing are measured using standard ASTM methods and conditions including ASTM D256, ASTM D638M-89 and ASTM D3764.
  • MA-SEBS is a maleated graft styrene/ethylene-butylene/styrene block copolymer (2 wt. percent maleic anhydride content)
  • MA/PO is an ethylene/octene copolymer having density of 0.863 g/cc and melt index of 0.5 modified with 1 wt. percent maleic anhydride
  • MA/PO is an ethylene/octene copolymer having density of 0.870 g/cc and melt index of 30 modified with 0.4 wt. percent maleic anhydride
  • PO with oil is an ethylene/octene copolymer having a density of 0.863 g/cc and melt index of 30 extended with oil (25 wt. percent)
  • SEBS is a styrene/ethylene-butylene/styrene copolymer containing 32 wt percent styrene
  • SEPS is a styrene/ethylene-propylene/styrene copolymer containing 65 wt. percent styrene
  • FAPPO is poly(2,6-dimethyl-p-phenylene ether) grafted with 1 -2 wt. percent fumaric acid
  • Irganox 1010 is 3,5-di-tert-butyl-4-hydroxy-neopentanetetraylester of hydrocinnamic acid
  • pTBBA-AI is aluminum tris(p-tert-butyl)benzoate
  • Table II summarizes the physical properties which are obtained. "MOE 95 percent” denotes the margin of error for each measurement at the 95 percent confidence level. "Izod” is the notched Izod toughness at room temperature. "Er” is the tensile elongation at rupture, 'Tr” is the tensile strength at rupture, and “Modulus” is the tensile modulus, all measured at room temperature.

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Abstract

L'invention concerne un mélange de polymères renfermant: a) un polymère aromatique de monovinylidène syndiotactique, b) un polyamide, c) un polymère compatible avec a) et b), d) un modificateur de résistance à base d'une polyoléfine caoutchouteuse, ce modificateur étant éventuellement étendu à l'huile, e) un polymère caoutchouteux formant un domaine, f) une polyoléfine caoutchouteuse fonctionnalisée par un groupe polaire, et éventuellement g) un polymère compatible avec a) et d).
PCT/US1998/017889 1997-09-12 1998-08-28 Melanges de polymeres durcis WO1999014273A1 (fr)

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AT98942286T ATE205235T1 (de) 1997-09-12 1998-08-28 Schlagzähe polymermischungen
EP98942286A EP1015517B1 (fr) 1997-09-12 1998-08-28 Melanges de polymeres durcis
CA002301701A CA2301701A1 (fr) 1997-09-12 1998-08-28 Melanges de polymeres durcis
DE69801587T DE69801587T2 (de) 1997-09-12 1998-08-28 Schlagzähe polymermischungen
JP2000511816A JP2001516786A (ja) 1997-09-12 1998-08-28 強靭化ポリマーブレンド
AU90379/98A AU9037998A (en) 1997-09-12 1998-08-28 Toughened polymer blends
KR1020007002583A KR20010023899A (ko) 1997-09-12 1998-08-28 강화 중합체 블렌드

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WO1999045547A1 (fr) * 1998-03-02 1999-09-10 The Dow Chemical Company Film de polymere syndiotactique aromatique a base de monovinylidene
WO2000047669A1 (fr) * 1999-02-09 2000-08-17 The Dow Chemical Company Compositions polymeres aromatiques de monovinylidene syndiotactiques renforcees en fibres, possedant un brillant eleve
WO2001012721A1 (fr) * 1999-08-12 2001-02-22 Ciba Specialty Chemicals Holdings Inc. Melanges polymeres a resistance accrue aux chocs
WO2003016685A1 (fr) * 2001-08-03 2003-02-27 Dow Global Technologies Inc. Systeme de carter d'huile fixe de façon adhesive au carter
US6543404B2 (en) 2001-04-04 2003-04-08 Dow Global Technologies, Inc. Adhesively bonded engine intake manifold assembly
DE10335889B3 (de) * 2003-08-06 2005-01-13 Rehau Ag + Co. Kupplungsleitung
WO2005033206A1 (fr) 2003-09-13 2005-04-14 Rehau Ag + Co Composition polymerique
WO2008156964A1 (fr) * 2007-06-13 2008-12-24 Sabic Innovative Plastics Ip B.V. Compositions de poly(arylène éther), procédés et articles
US8975329B2 (en) 2011-12-02 2015-03-10 Sabic Global Technologies B.V. Poly(phenylene ether) articles and compositions
US20160300639A1 (en) * 2015-04-10 2016-10-13 Samsung Sdi Co., Ltd. Electrically Conductive Polyamide/Polyphenylene Ether Resin Composition and Molded Article for Vehicle Using the Same
US20160326369A1 (en) * 2014-01-09 2016-11-10 Samsung Sdi Co., Ltd. Conductive Polyamide/Polyphenylene Ether Resin Composition and Automotive Molded Article Manufactured Therefrom

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KR20030040480A (ko) 2000-09-22 2003-05-22 이 아이 듀폰 디 네모아 앤드 캄파니 개선된 난연성 폴리아미드 조성물
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US7201915B2 (en) * 2003-10-10 2007-04-10 International Flavors & Fragrances Inc. Polyamide stick dispensing product and method of use
EP1773942A1 (fr) * 2004-07-29 2007-04-18 Solvay Advanced Polymers, L.L.C. Compositions de polyamide antichoc
US20090048402A1 (en) * 2007-08-17 2009-02-19 Lynch Michael W Preparing multimodal polyethylene having controlled long chain branching distribution
DE102008016436A1 (de) * 2008-03-31 2009-10-01 Ems-Patent Ag Polyamidformmasse für lackfreie, zähe Gehäuse mit Hochglanz-Oberfläche
FR2953849B1 (fr) * 2009-12-16 2012-11-16 Rhodia Operations Composition polyamide de faible conductivite thermique
MX365310B (es) * 2010-03-08 2019-05-29 Ube Industries Composición de resina de poliamida.
WO2011118617A1 (fr) * 2010-03-26 2011-09-29 宇部興産株式会社 Composition de résine polyamide pour partie coulissante, partie coulissante et procédé de production d'une partie coulissante et d'une automobile
CN105524461B (zh) * 2016-01-05 2018-02-02 广州市聚赛龙工程塑料股份有限公司 一种耐汽油玻纤增强无卤阻燃sPS复合材料及其制备方法
CN116802232A (zh) * 2021-02-01 2023-09-22 陶氏环球技术有限责任公司 聚酰胺组合物

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Cited By (19)

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Publication number Priority date Publication date Assignee Title
WO1999045547A1 (fr) * 1998-03-02 1999-09-10 The Dow Chemical Company Film de polymere syndiotactique aromatique a base de monovinylidene
WO2000047669A1 (fr) * 1999-02-09 2000-08-17 The Dow Chemical Company Compositions polymeres aromatiques de monovinylidene syndiotactiques renforcees en fibres, possedant un brillant eleve
WO2001012721A1 (fr) * 1999-08-12 2001-02-22 Ciba Specialty Chemicals Holdings Inc. Melanges polymeres a resistance accrue aux chocs
US6444754B1 (en) 1999-08-12 2002-09-03 Ciba Specialty Chemicals Corporation Polymer blends with improved impact resistance
US6765062B2 (en) 1999-08-12 2004-07-20 Ciba Specialty Chemicals Corporation Polymer blends with improved impact resistance
US6543404B2 (en) 2001-04-04 2003-04-08 Dow Global Technologies, Inc. Adhesively bonded engine intake manifold assembly
WO2003016685A1 (fr) * 2001-08-03 2003-02-27 Dow Global Technologies Inc. Systeme de carter d'huile fixe de façon adhesive au carter
EP1510743A2 (fr) * 2003-08-06 2005-03-02 REHAU AG + Co Conduit tubulaire de raccordement
DE10335889B3 (de) * 2003-08-06 2005-01-13 Rehau Ag + Co. Kupplungsleitung
EP1510743A3 (fr) * 2003-08-06 2005-10-26 REHAU AG + Co Conduit tubulaire de raccordement
WO2005033206A1 (fr) 2003-09-13 2005-04-14 Rehau Ag + Co Composition polymerique
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US8975329B2 (en) 2011-12-02 2015-03-10 Sabic Global Technologies B.V. Poly(phenylene ether) articles and compositions
US20160326369A1 (en) * 2014-01-09 2016-11-10 Samsung Sdi Co., Ltd. Conductive Polyamide/Polyphenylene Ether Resin Composition and Automotive Molded Article Manufactured Therefrom
US20190085165A1 (en) * 2014-01-09 2019-03-21 Lotte Advanced Materials Co., Ltd. Conductive Polyamide/Polyphenylene Ether Resin Composition and Automotive Molded Article Manufactured Therefrom
US10273361B2 (en) * 2014-01-09 2019-04-30 Lotte Advanced Materials Co., Ltd. Conductive polyamide/polyphenylene ether resin composition and automotive molded article manufactured therefrom
US20160300639A1 (en) * 2015-04-10 2016-10-13 Samsung Sdi Co., Ltd. Electrically Conductive Polyamide/Polyphenylene Ether Resin Composition and Molded Article for Vehicle Using the Same
US10056168B2 (en) * 2015-04-10 2018-08-21 Lotte Advanced Materials Co., Ltd. Electrically conductive polyamide/polyphenylene ether resin composition and molded article for vehicle using the same

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AU9037998A (en) 1999-04-05
KR20010023899A (ko) 2001-03-26
JP2001516786A (ja) 2001-10-02
DE69801587T2 (de) 2002-04-11
EP1015517A1 (fr) 2000-07-05
CA2301701A1 (fr) 1999-03-25
US5990244A (en) 1999-11-23
ATE205235T1 (de) 2001-09-15
TW418237B (en) 2001-01-11
CN1269815A (zh) 2000-10-11
MY114820A (en) 2003-01-31
DE69801587D1 (de) 2001-10-11
EP1015517B1 (fr) 2001-09-05

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